Oxyalkylated aliphatic polyepoxidetreated amine-modified phenol aldehyde resins, and method of making same



United States Patent lice ,atemed figffifi 30, 1953, now U. S. Patent2,771,452.

dated 'January 8, 1952, to Zech. This particular last 2, 54,798mentioned patent describes a composition of the followin eneral formula:OXYALKYLATED ALIPHATIC POLYEPOXIDE- g g 0 TREATED AMlNE-MODIFIED PHENOLALDE- HYDE RESINS, AND METHOD OF MAKING SAME Melvin De Groote, St.Louis, and Kwan-Ting Shen, Brent- R wood, Mo., assignors to PetroliteCorporation, Wilmington, Del., a corporation of Delaware 10-OCHZ?H-O:CHICH2 No Drawing. Original application July 30, 1953, SerialE No. 371,411, now Patent No. 2,771,452, datesd Novem- Halogen z bet1956 Divided and this application emember in which x is at least 1 zvaries from less than 1 to 1956 smalNo' 610699 15 more than 1, and -xand z together are' at least 2 and 7 Claims. (Cl. 260-45) 1 not morethan 6, and R is the residue of the polyhydric alcohol remaining afterreplacement of at least 2 of the The present invention is acontinuation-in-part of our hydroxyl groups thereof with the f f ethergroups co-pending application, Serial No. 364,502, filed June of P abqveformula and any'remammg re the 26, 1953, now U. s. Patent 2,771,426, anda division of resldue being free Y Y groupsour e di a ti Se 1N 371,411,r d Jul It is obvious from what'is said in the patent that c P n ng pplea on ma 0 e y variants can be obtained in which the halogen isreplaced Our invention is concerned with new chemical proda hydroxylradical; thus the formulaxwouldl ucts or compounds useful asdemulsifying agents in proc- 0 esses or procedures particularly adaptedfor preventing, 1 breaking or resolving emulsions of the water-in-oiltype and particularly petroleum emulsions. Our invention is alsoconcerned with the application of such chemical products or compounds invarious other arts and indusfi, tries as well as with method ofmanufacturing the new chemical products of compounds which are ofoutstanding value in demulsification. H z

The Presellt invention is concerned With a three-Stet3 Reference tobeing thermoplastic characterized them mamlfaeilh'ihg method involvingcondensing certain as being liquids at ordinary temperature or readilyconphenol aldehyde resins, hereinafter described in detail, tibl tliquids b merely heatin below the pointof with certain basichydrcXylated secondary mcncamines, pyrolysis and thus differentiatesthem from infusible hereinafter described ill detail, and formaldehyde;resins. Reference to being soluble in an organic solvent oXyalkylatlollof the Condensation Product h Certain means any of the usual organicsolvents such as alcohols, noharyl hydI'oPhlle P y p hereinafterdescribed in ketones, esters, ethers, mixed solvents, etc. ,Referencedetail; and oxyalkylailon of the Previously oXyalkyl' to solubility ismerely to differentiate from a reactant aied resin Condensate withCertain mohoePoXldeS, also which is not soluble and might be not onlyinsoluble but hereinafter described in detail. also infusible.Furthermore, solubility is a factor inso- T pr n nv n n is h r r z yanalogous far that it sometimes is desirable to dilute the compoundcompounds derived from diglycidyl ethers which do not containing theepoxy rings before reacting with an amine introduce any hydrophoheProperties in its usudl meah- 5 condensate. In such instances, ofcourse, the solvent ihg in feet, are more p to introduce hydrophlleselected would have to be one which is not susceptible to P OPeTtleS-Thus, the dlePOXldeS p y in the Present oxyalkylation as, for example,kerosene, benzene, toluene, invention are characterized by the fact thatthe divalent dioxane, possibly various ketones, chlorinated solvents,radical connecting the terminal epoxide radicals contains dibutyl ether,dihexyl ether, ethyleneglycol di'ethylether, less than 5 carbon at ms inan unin rrupte h ndiethyleneglycol diethylether, anddimethoxytetraethylene- The diepoxides employed in the present processare l l, obtained from glycols such as ethylene glycol, diethylene Theexpression epoxy is not usually limited to the y p py g y p py n gly prpyl n 1,2-epoxy ring. The 1,2-epoxy ring is sometimes rey s' y idiglycerol, y h and Similar ferred to as the oxirane ring to distinguishit from other pounds. Such products are Well known and are charepoxyrings. Hereinafter the word epoxy unless indiacterized by the fact thatthere are not more than 4 uninr d otherwise, ill b u ed to mean theoxiran ring, terrupted carbon atoms in any group which is part of i, the1,2-epoxy ring. Furthermore, where a comthe l'adleel j i the epoxide Pof necessity Such pound has two or more oxirane rings they will berediepoxides must be nonaryl or aliphatic in character. f ed t aspolyepoxides. They usually represent, of The diglycidyl ethers ofco-pending application, Serial course, 1,2-epoxide rings or oxiranerings in the alphaare invariably and inevitably y in romega position.This is a departure, of course, from the acter. standpoint of strictlyformal nomenclature as in'the" ex- The dlePoXldeS p y in the p Processare ample of the simplest diepoxide which contains atleast usuallyobtained by reacting a glycol or equivalent com- 4 carbon atoms and isformally described as 1,2-epoxypound, such as glycerol or diglycerol,with epichloro- 3,4-epoxybutane(l,2-3,4 diepoxybutane). hydrin andsubsequently with an alkali. Such diepoxides It well may be that eventhough the previously sughave been described in the literature andparticularly gested formula represents the principal component, or

the patent literature. See, for example, Italian Patent components, ofthe resultant or reaction product de- No. 400,973, dated August 8, 1951;see, also, British scribed in the previous text, it may be important tonote Patent 518,057, dated December 10, 1938; and U. S. that somewhatsimilar compounds, generally of much Patent No. 2,070,990, datedFebruary 16, 1937, to Gross higher molecular weight, have been describedas comet al. Reference is made also to U. S. Patent 2,581,464, plexresinous epoxides which arenpolyether derivatives of polyhydriccompounds containing an average of more than one epoxide group permolecule and free from functional groups other than epoxide and hydroxylgroups. The compounds here included are limited to the monomers or thelow molal members of such series and generally contain two epoxide ringsper molecule and may be entirely free from a hydroxyl group. This isimportant because the instant invention is directed towards productswhich are not insoluble resins and have certain solubilitycharacteristics not inherent in the usual thermosetting resins. Simplyfor purpose of illustration to show a typical diglycidyl ether of thekind herein employed, reference is made to the following formula:

or if derived from cyclic diglycerol the structure would be thus:

or the equivalent compound wherein the ring structure involves only 6atoms, thus:

I HOB.

1 H Hc-O-(frt HCO-CH H l H 3H l Commercially available compounds seem tobe largely the former with comparatively small amounts, in fact,comparatively minor amounts, of the latter.

Having obtained a reactant having generally 2 epoxy rings as depicted inthe next to last formula preceding, or low molal polymers thereof, itbecomes obvious the reaction can take place with any amine-modifiedphenolaldehyde resin by virtue of the fact that there are always presentreactive hydroxyl groups which are part of the phenolic nuclei and theremay be present reactive hydrogen atoms attached to a nitrogen atom, oran oxygen atom, depending on the presence of a hydroxylated group orsecondary amino group.

To illustrate the products which represent the subject matter of thepresent invention reference will be made to a reaction involving a moleof the oxyalkylating agent, 1. e the compound having two oxirane ringsand an amine condensate. Proceeding with the example previouslydescribed it is obvious the reaction ratio of two moles of the aminecondensate to one mole of the oxyalkylating agent gives a product whichmay be indicated as follows:

(Condensate) (Condensate) in which n is a small whole number less than10, and usually less than 4, and including 0, and R represents adivalent radical as previously described being free from any radicalhaving more than 4 uninterrupted carbon atoms in a single chain, and thecharacterization condensate is simply an abbreviation for the condensatewhich is described in greater detail subsequently.

Such intermediate product in turn also must be soluble but solubility isnot limited to an organic solvent but may include Water, or for thatmatter, a solution of water containing an acid such as hydrochloricacid, acetic acid, hydroxyacetic acid, gluconic acid, etc. In otherwords, the nitrogen groups present, whether two or more, may or may notbe significantly basic and it is immaterial whether aqueous solubilityrepresents an anhydro base or the free base (combination with water) ora salt form such as the acetate, chloride, etc. The purpose in theinstance is to differentiate from insoluble resinous materials,particularly those resulting from gelation or cross-linking. Not onlydoes this property serve to differentiate from instances where aninsoluble material is desired but also serves to emphasize the fact thatin many instances the preferred compounds have distinct watersolubilityor are distinctly dispersible in 5% gluconic acid. For instance, theproducts freed from any solvent can be shaken with 5 to 20 times theirweight of 5% gluconic acid at ordinary temperature and show at leastsome tendency towards being self-dispersing. The solvent which isgenerally tried is xylene. If xylene alone does not serve then a mixtureof xylene and methanol, for instance, parts of xylene and 20 parts ofmethanol, or 70 parts of xylene and 30 parts of methanol, can be used.Sometimes it is desirable to add a small amount of acetone to thexylene-methanol mixture, for instance,

5% to 10% of acetone.

A mere examination of the nature of the products before and aftertreatment with a polyepoxide reveals that the polyepoxide by and largeintroduces increased hydra phile character or, inversely, causes adecrease in hydrophobe character. However, the solubilitycharacteristics of the final product, i. e., the product obtained byoxyalklation with a monepoxide, may vary all over the map. This isperfectly understandable because ethylene oxide, glycide, and to alesser extent methyl glycide, introduce predominantly hydrophilecharacter, while propylene oxide and more especially butylene oxide,introduce primarily hydrophobe character. A mixture of the variousoxides will produce a balancing in solubility characteristics or in thehydrophobe-hydrophile character so as to be about the same as prior tooxyalkylation with the monoepoxide.

The oxyalkylated polyepoxide treated condensates obtained in the mannerdescribed are, in turn, oxyalkylationsusceptible and valuablederivatives can be obtained by further reaction with other alkyleneoxides, for instance, styrene oxides (phenylethylene oxide),cyclohexylethylene oxide, ethylene imine, propylene imine,acrylonitrile, etc.

Similarly, the oxyalkylated polyepoxide-derived compounds can be reactedwith a product having both a nitrogen group and a 1,2-epoxy group, suchas 3-dialkylaminoepoxypropane. See U. S. Patent No. 2,520,093, datedAugust 22, 1950, to Gross.

Although the herein described products have a number of industrialapplications, they are of particular value for resolving petroleumemulsions of the water-in-oil type that are commonly referred to as cutoil, roily oil," emulsified oil, etc., and which comprise fine dropletsof naturally-occurring Waters or brines dispersed in a more or lesspermanent state throughout the oil which Constitutes the continuousphase of the emulsion.

The new products are useful as wetting, detergent and leveling agents inthe laundry, textile and dyeing industries; as wetting agents anddetergents in the acid washing of building stone and brick; as wettingagents and spreaders in the application of asphalt in road building andthe like; as a flotation reagent in the flotation separation of variousaqueous suspensions containing negacombinationwith water or particularlyin the form of a low molal organic acid salt such as the gluconates orthe acetate or hydroxyacetate, have sufficiently hydrophile character toat least meet the test set forth in U. S. Patent No. 2,499,368, datedMarch 7, 1950, to De Groote et al. In said patent such test foremulsification using a water-insoluble solvent, generally xylene, isdescribed as an index of surface activity.

In the present instance the various condensation products as such or inthe form of the free base or in the form of the acetate, may notnecessarily be xylene-soluble although they are in many instances. Ifsuch compounds are not xylene-soluble the obvious chemical equivalent orequivalent chemical test can be made by simply using some suitablesolvent, preferably a water-soluble solvent such as ethylene-glycoldiethylether, or a low molal alcohol, or a mixture to dissolve theappropriate product being examined and then mix with the equal weight ofxylene, followed by addition of water. Such test is obviously the samefor the reason that there will be two phases on vigorous shaking andsurface activity makes its presence manifest. It is understood thereference in the hereto appended claims as to the use of xylene in theemulsification test includes such obvious variant.

For purpose of convenience what is said hereinafter will be divided intoeight parts:

Part 1 is concerned with the hydrophile nonaryl polyepoxides andparticularly diepoxides employed as reactants;

Part 2 is concerned with the phenol-aldehyde resin which is subjected tomodification by condensation to yield the amine-modified resin;

Part 3 is concerned with appropriate basic hydroxylated secondary amineswhich may be employed in the preparation of the herein-describedamine-modified resins;

Part 4 is concerned with reactions involving the resin, the amine, andformaldehyde to produce specific products or compounds which are thensubjected to reaction with polyepoxides, and particularly diepoxides;

Part 5 is concerned with reactions involving the two preceding types ofmaterials and examples obtained by such reaction. Generally speaking,this involves nothing more than reaction between 2 moles of a previouslyprepared amine-modified phenol-aldehyde resin condensate as describedand one mole of a hydrophile polyepoxide so as to yield a new and largerresin molecule, or comparable product;

Part 6 is concerned with the use of a monoepoxide in oxyalkylating theproducts described in Part 5, preceding, i. e., those derived by meansof reaction between a polyepoxide and an amine-modified phenol-aldehyderesin as described;

Part 7 is concerned with the resolution of petroleum emulsions of thewater-in-oil type by means of the previously described chemicalcompounds or reaction products; and

Part 8 is concerned with uses for the products herein described, eitheras such or after modification, including any applications other thanthose involving resolution of petroleum emulsions of the water-iu-oiltype.

PART 1 Reference is made to previous patents as illustrated in themanufacture of the nonaryl polyepoxides and particularly diepoxidesemployed as reactants in the instant invention. The simplest diepoxideis probably the one derived from 1,3-butadiene or isoprene. Suchderivatives are obtained by the use of peroxides or by other suitablemeans and the diglycidyl ethers may be indicated thus:

In some instances the compounds are essentially derivatives of etherizedepiehlorohydrin or methyl epiehlorohydrin. Needless to say, suchcompounds can be derived from glycerol monochlorohydrin by etherizationprior to ring closure. An example is illustrated in the pre viouslymentioned Italian Patent No. 400,973:

Another type of diepoxide is diisobutenyl dioxide as described inaforementioned U. S. Patent No. 2,070,990, dated February 16, 1937, toGroll, and is of the following formula:

The diepoxides previously described may be indicated by the followingformula:

in which R represents a hydrogen atom or methyl radical and R"represents the divalent radical uniting the two terminal epoxide groups,and n is the numeral 0 or 1. As previously pointed out, in the case ofthe butadiene derivative, n is 0. In the case of diisobutenyl dioxide R"is CH CH and n is 1. In another example previously referred to R is CHOCH and n is 1.

However, for practical purposes the only diepoxide available inquantities other than laboratory quantities is a derivative of glycerolor epiehlorohydrin. This particular diepoxide is obtained fromdiglycerol which is largely acyclic diglycerol, and epichlorohydrin orequivalent thereof in that the epichlorhydrin itself may supply theglycerol or diglycerol radical in addition to the epoxy rings. As hasbeen suggested previously, instead of starting with glycerol or aglycerol derivative, one could start with any one of a number of glycolsor polyglycols and it is more convenient to include as part of theterminal oxirane ring radical the oxygen atom that was derived fromepiehlorohydrin or, as might be the case, methyl in the above formula Ris selected. from groups such as the following:

It is to be noted that in the above epoxides there is a complete absenceof (a) aryl radicals and (b) radicals in which 5 or more carbon atomsare united in a single uninterrupted single group. R is inherentlyhydrophilein character as indicated by the fact that it is specifiedthatthe precursory diol or polyol OHROH must be water soluble insubstantially all proportions, i. e., water miscible.

Stated another way, what is said previously means that a polyepoxidesuch as is derived actually or theoretically, or at least derivable fromthe diol. I-IOROH, in which the oxygen-linked hydrogen atoms werereplaced by Thus, R(OH),,, where n represents a small whole number whichis 2 or more, must be water-soluble. Such limitation excludespolyepoxides if actually derived or theoretically derived at least, fromwater-insoluble diols or water-insoluble triols or higher polyols.Suitable polyols may contain as many as 12 to 20 carbon atoms orthereabouts.

Referring to a compound of the type above in the formula H H H E H HC--CC-[R1]OCCCH in which R is C H (OH) it is obvious that reaction withanother mole of epichlorohydrin with appropriate ring closure wouldproduce a triepoxide or, similarly, if R happened to be C H (OH)OC H(OH), one could obtain a tetraepoxide. Actually, such proceduregenerally yields triepoxides, or mixtures with higher epoxides andperhaps in other instances mixtures in which diepoxides are alsopresent. Our preference is to use the diepoxides.

There is available commercially at least one diglycidyl ether. free fromaryl groups and also free from any radical having 5 or more carbon atomsin an uninterrupted chain. This particular diglycidyl ether is obtainedby the use of epichlorohydrin in such a manner that approximately 4moles of epichlorohydrin yield one mole of the diglycidyl ether, orstated another way, it can be considered as being formed from one moleof diglycerol and 2 moles of epichlorohydrin so as to give theappropriate diepoxide. The molecular weight is approximately 370 and thenumber of epoxide groups per molecule are approximately 2. For thisreason in the. first of a series of subsequent examples this particulardiglycidyl ether is used, although obviously any of the otherspreviously described would be just as suitable. For convenience, thisdiepoxide will be referred to as diglycidyl ether A. Such materialcorresponds in a general. way to the previous formula.

Using laboratory procedure we have reacted diethylene:

glycol with epichlorohydrin and subsequently with alkali so as toproduce a product which, on examination, corresponded approximately tothe following compound:

The molecular weight of the product was. assumed to be 230 and theproduct was available in laboratory quantities only. For this reason,the subsequent table referring to the use of this particular diepoxide,which will be referred to as diglycidyl ether B, is in grams instead ofpounds.

Probably the simplest terminology for these polyepoxides, andparticularly diepoxides, to difierentiate from comparable aryl compoundsis to use the terminology 'epoxylalkanes and, more particularly,polyepoxyalkanes or diepoxyalkanes. The diificulty is that the majorityof these compounds represent types in which a carbon atom chain isinterrupted by an oxygen atom and, thus, they are not strictly alkanederivatives. Furthermore', they may be hydroxylated or represent aheterocyclic'ring. The principal class properly may be referred to aspolyepoxypolyglycerols, or diepoxypolyglycerols.

Other examples of diepoxides involving a heterocyclic ring having, forexample, 3 carbon atoms and 2 oxygen atoms are obtainable by theconventional reaction of combining erythritol with a carbonyl compound,such as formaldehyde or acetone, so as to form the 5-membered ring,followed by conversion of the terminal hydroxyl groups into epoxyradicals.

Also see Canadian Patent No. 672,935.

PART 2 It is well known that one can readily purchase on the open marketor prepare fusible organic solvent-soluble, water-insoluble resinpolymers of a composition approximated in an idealized form by theformula In the above formula n represents a small whole number varyingfrom 1 to 6, 7, or 8, or more, up to probably 10 or 12 units,particularly when the resin is subjected to heating under a vacuum asdescribed in the literature. A limited sub-genus is in the instance oflow molecular weight polymerswhere the total number of phenol nucleivaries from 3 to 6, i. e., n varies from 1 to 4, R represents analiphatic hydrocarbon substituent, generally an alkyl radical havingfrom 4 to 15 carbon atoms, such as butyl, amyl, hexyl, decyl or dodecylradical. Where the divalent bridge radical is shown as being derivedfrom formaldehyde it may, of course, be derived from any other reactivealdehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it isnecessarily soluble in any organic solvent. This is particularly truewhere the resins are derived from trifunctional phenols as previouslynoted. However, even when obtained from a difunctional phenol, forinstance, paraphenylphenol, one may obtain a resin which is not solublein a nonoxygenated solvent, such as benzene, or xylene, but requires anoxygenated solvent such as a low molal alcohol, dioxane, ordiethyleneglycol diethylether. Sometimes a mixture of the two solvents(oxygenated and non-oxygenated) will serve. See Example 9a of U. S.Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser.

The resins herein employed as raw materials must be soluble in anonoxygenated solvent, such as benzene or xylene. This presents noproblem insofar that all that is required is to make a solubility teston commercially available resins, or else prepare resins which arexylene or benzene soluble as described in aforementioned U. S. PatentNo. 2,499,365, or in U. S. Patent No. 2,499,368, dated March 7, 1950, toDe Groote and Keiser.

If one selected a resin of the kind just described previously andreacted approximately one mole of the resin with two moles offormaldehyde and two moles of a basic hydroxylated secondary amine asspecified, following the same idealized over-simplification previouslyreferred to, the resultant product might be illustrated thus:

basic hydroxylated amine may be designated thus:

In conducting reactions of this kind one does not necessarily obtain ahundred percent yield for obvious reasons. Certain side reactions maytake place. For instance, 2 moles of amine may combine with one mole ofthe aldehyde, or only one mole of the amine may combine with the resinmolecule, or even to a veryslight extent, if at all, 2 resin units maycombine without any amine in the reaction product, as indicated in thefollowing formulas:

As has been pointed out previously, as far as the resin unit goes onecan use a mole of aldehyde other than formaldehyde, such asacetaldehyde, propionaldehyde or butyraldehyde. The resin unit may beexemplified thus:

in which R' is the divalent radical obtained from the particularaldehyde employed to form the resin. For reasons which are obvious thecondensation product obtained appears to be described best in terms ofthe method of manufacture.

Resins can'be made using an acid catalyst or basic catalyst or acatalyst having neither acid nor basic properties in the ordinary senseor without any catalyst at all. It is preferable that the resinsemployed be substantially neutral. In other words, if prepared by usinga strong acid as a catalyst, such strong acid should be neutralized.Similarly, if a strong base is used as a catalyst it is preferable thatthe base be neutralized although we have found that sometimes thereaction described proceeded more rapidly in the presence of a smallamount of a free base. The amount may be as small as a 200th of apercent and as much as a few l0ths of a percent. Sometimes moderateincrease in caustic soda and caustic potash may be used. However, themost desirable procedure in practically every case is to have the resinneutral.

In preparing resins one does not get a single polymer, i. e., onehavingjust 3 units, or just 4 units, or just 5 units, or just 6 units, etc. Itis usually a mixture; for instance, one approximating 4 phenolic nucleiwill have some trimer and pentamer present. Thus, the molecular weightmay be such that it corresponds to a fractional value for n as, forexample, 3.5, 4.5 or 5.2.

"In the actual manufacture of the resins we found no reason for usingother than those which are lowest in price and most readily availablecommercially. For purpose of convenience suitable resins arecharacterized in the following table:

Table I x R Mfol. wt.

o resin ample R zf fi derived n molecule number 0mased on n+2) Tertiarybutyl Para Formal- 3. 5 882. 5

Secondary bntyl. 3. 5 882. 5 Tertiary arnyl 3. 5 959. 5 Mixed secondary3. 5 805. 5

and tertiary amyl.

3. 5 1, 022. 5 Nonyl 3. 5 1, 330. 5 Tertiary butyl 3. 5 1, 071. 5

Tertiary amyl 3. 5 1, 148. 5 Nonyl do. 0 3. 5 1. 456.5 Tertiary butyl oPropional- 3. 5 1, 008.5

dehyde. Tertiary amyl 3. 5 1, 085. 5 Nonyl 3. 5 1, 393. 5 Tertiary butyl4. 2 996. 6

4. 2 1, 083. 4 on 4. 2 1, 430. 6 Tertiary but 4. 8 1, 094. 4 Tertiaryamyl. 4.8 1, 189. 6 4. 8 l, 570. 4 1. 5 604.0 1. 5 653.0 1. 5 688. 0

PART 3 As has been pointed out previously the amine herein employed as areactant is a basic hydroxylated secondary monoamine whose compositionis indicated thus:

in which R represents a monovalent alkyl, alicyclic, arylalkyl radicalwhich may be heterocyclic in a few instances as in a secondary aminederived from furfurylamine by reaction of ethylene oxide or propyleneoxide. Furthermore, at least one of the radicals designated by R musthave at least one hydroxyl radical. A large number of secondary aminesare available and may be suitably em ployed as reactants for the presentpurpose. Among others, one may employ diethanolamine, methylethanolamine, dipropanolamine and ethylpropanolamine. Other suitablesecondary amines are obtained, of course, by taking any suitable primaryamine, such asan alkylamine an arylalkylamine, or an alicyclic amine,and treating the amine with one mole of an oxyalkylating agent, such asethylene oxide, propylene oxide, butylene oxide, glycide, ormethylglycide. Suitable primary amines which can be so convertedintosecondary amines, include butylamine, amylamine, hexylamine, highermolecular weight amines derived from fatty acids, cyclohexylamine,benzylamine, furfurylamine, etc. In other instances primary amines whichhave at least one hydroxyl radical can be treated similarly with anoxyalkylating agent, or, for that matter, with an alkylatingagent suchas benzylchloride, esters of chloracetic acid, alkyl bromides,dimethylsulfate, esters of sulfonic acid, etc., so as to convert theprimary amine into a secondary amine. Among others, such amines includeZ-amin-I-butanol, 2-amino-2- methyl-l-propanol,2-amino-2-methyl-1,3-propanediol, 2-

11 amino 2 ethyl 1,3 propanediol, and trie-(hydroxy-InethyD-aminomethane; Another example of such amines isillustrated by4-amino-4-methyl-2-pentanol.

Similarly, one can prepare suitable secondary amines which have not onlya hydroxyl group but also one or more divalent oxygen linkages as partof an ether radical. Examples of such compounds are:

HOCzHt (041100 CHzCH(CHa) (CH3) CHCHz) NH HO CzH4 (C1130 CHzCH2O CHQGHZOCHQCHz) HoCrHa (CHaO CHzCHsCHzCHzCHzCHz) /NH' HO C1114 or comparablecompounds having two hydroxylated groups of different lengths as in (H0CHQCHZO CHzCHzOCHzOHe) HOC2H4 Other examples of suitable amines includealpha-methylbenzylamine and monoethanolamine; also amines obtained bytreating cyclohexylmethylamine with one mole of an oxyalkylating agentas previously described; betaethylhexyl-butanolamine, diglycerylamine,etc. Another type of amine which is of particular interest because itincludees a very definite hydrophile group includes sugar amines such asglucamine, galactamine and fructamine, such as N-hydroxyethylglucamine,N-hydroxyethylgalac tamine, and N-hydroxyethylfructamine.

Other suitable amines may be illustrated by CH; HO.CH2..CHzOH 11mHO.CH:..CHzOH lHa om. .ornon onaiiornon See, also, correspondinghydroxylated amines which can be obtained from rosin or similar rawmaterials and described in U. S. Patent No. 2,510,063, dated June 6,1950, to Bried. Still other examples are illustrated by treatment ofcertain secondary amines, such as the following, with a mole of anoxyalkylating agent as described; phenoxyethylamine, phenoxypropylamine,phenoxyalphamethylethylamine, and phenoxypropylamine.

Other procedures for production of suitable compounds having a hydroxylgroup and a single basic amino nitrogen atom can be obtained from anysuitable alcohol or the like by reaction with a reagent which containsan epoxide group and a secondary amine group. Such reactants aredescribed, for example, in U. S. Patent Nos. 1,977,251 and 1',9-7-7,253,bothdated October 16, 1934, to Stallmann.

12 Among the reactantsudescribed in said latter patent are thefollowing:

oH,-oHoH-NH-cm PART 4 The products obtained by the herein describedprocesses represent cogeneric mixtures which are the result of acondensation reaction or reactions. Since the resin molecule cannot bedefined'satisfactorily by formula, although it may be so illustrated inan idealized simplification, it is difiicult to actually depict thefinal product of the cogeneric mixture except in terms of the processitself.

Previous reference has been made to the fact that the procedure hereinemployed is comparable, in a general way, to that which corresponds tosomewhat similar derivatives made either from phenols as differentiatedfrom a resin, or in the manufacture of a phenol-amine-aldehyde resin; orelse from a particularly selected resin and an amine and formaldehyde inthe manner described in Bruson Patent No. 2,031,557 in order to obtain aheatreactive resin. Since the condensation products obtained are notheat-convertible and since manufacture is not re-.

stricted to a single phase system, and since temperatures up to C. orthereabouts may be employed, it is obvious that the procedure becomescomparatively simple. Indeed, perhaps no description is necessary overand above what has been said previously, in light ofsubsequent examples.details are included;

A convenient piece of equipment for preparation of these cogenericmixtures is a resin pot of the kind described in aforementioned U. S.Patent No. 2,499,368. In most instances the resin selected is not: aptto be a fusible liquid at the early or low temperature stage of reactionif employed as subsequently described; in fact, usually it is apt to bea solid at distinctly higher temperatures, for instance, ordinary roomtemperature.

Thus, we have found it convenient to use a solvent and in a polyphasesystem. However, if desirable,.one1can:

use an oxygenated solvent such asa low-boilingalcohol, including ethylalcohol, methyl, alcohol, etc. Higher alcohols can be used or one can.use a comparatively nonvolatile solvent such as dioxane or thediethyletherz of ethyleneglycol. One can also usea mixture of benzene orxylene and such oxygenated solvents. Note that the use of suchoxygenated solvent is not required in the sense that it is not necessarytouse an initial:resin;which.

is soluble only in anoxygenated solvent as inst ucted, and it is notnecessary to have a single phase -systemtfor. reaction.

Actually, water is apt to be present as'a solvent for thereason that inmost cases. aqueous formaldehyde. is em? ployed, which may bethecommercial productwhich is approximately 37%, or it' may be diluteddown to about 30% formaldehyde. However, paraformaldehyde. can be usedbut it is more difiicult perhaps to addto solid material instead of theliquid solution and, everything else- In any event, water is present aswater of reaction Ifthe.

beingequal, the latter: is apt to-bemore economical.

However, for purpose of clarity the following,

solvent is completely removed at the end of the process, no problem isinvolved if the material is used for any subsequent reaction.

In the next succeeding paragraph it is pointed out that frequently it isconvenient to eliminateall solvent, using atemperature of not over 150C. and employing vacuum, if required. This applies, of course, only tothose circumstances where it is desirable or necessary to remove thesolvent. Petroleum solvents, aromatic solvents, etc. can be used. Theselection of solvent, such as benzene xylene, or the like, dependsprimarily on cost, i. e., the use of the most economical solvent andalso on three other factors, two of which have been previouslymentioned; (a) is the solvent to remain in the reaction mass withoutremoval? (b) is the reaction mass to be subjected to further reaction inwhich the solvent, for instance, an alcohol, either low boiling or highboiling, might interfere'as in the case of oxyalkylatiorfl; and

the third factor is this, (c) is an elfort to be made to purify thereaction mass by the usual procedure as, for example, a water-wash toremove any unreacted low molal soluble amine, if employed and presentafter reaction? Such procedures are well known and, needless to say,certain solvents are more suitable than others. Everything else beingequal, we have found xylene the most satisfactory solvent.

We have found no particular advantage in using a low temperature in theearly stage of the'reaction because,

and for reasons explained, this is not necessary although it does applyin some other procedures that, in a general way, bear some similarity tothe present procedure.

There is no objection, of course, to giving the reaction an opportunityto proceed as far as it will at some low temperature, for instance, 30to 40 but ultimately one must employ the higher temperature in order toobtain products of the kind herein described. If a lower temperaturereaction is used initially the period is not critical, in fact, it maybe anything from a few hours up to 24 hours. We have not found any casewhere it was necessary or even desirable to hold the low temperaturestage for more than 24 hours. In fact, we are not convinced there is anyadvantagein holding it at this stage for more than 3 or 4 hours at themost. This, again, is a matter of convenience largely for one reason. Inheating and stirring the reaction mass there is a tendency forformaldehyde to be lost. Thus, if the reaction can be conducted at alower temperature, then the amount of unreacted formaldehyde isdecreased subsequently and makes it easier to prevent any loss. Here,again, this lower temperature is not necessary by virtue of heatconvertibility as previously referred to.

If solvents and reactants are selected so the reactants and products ofreaction are mutually soluble, then agitation is required only to theextent that it helps cooling or helps distribution of the incomingformaldehyde. This mutual solubility is not necessary as previouslypointed out but may be convenient under certain circumstances. On theother hand, if the products are not mutually soluble then agitationshould be more vigorous for the reason that reaction probably takesplace principally at the interfaces and the more vigorous the agitationthe more interfacial area. The general procedure employed is invariablythe same when adding the resin and the selected solvent, such as benzeneor xylene. Refluxing should be long enough to insure that the resinadded, preferably in a powdered form, is completely soluble. However, ifthe resin is prepared as such it may be added in solution form, just aspreparation is described in aforementioned U. S. Patent 2,499,368. Afterthe resin is in complete solution the amine is added and stirred.Depending on the amine selected, it may or may not be soluble in theresin solution. If it is not soluble in the resin solution it may besoluble in the aqueousformaldehydev solution. If so, the

reaction mass could be a three-phase system instead of a two-phasesystem although this would be extremely unusual. This solution, ormechanical mixture, if not completely soluble is cooled to at least thereaction temperature or somewhat below, for example 35 C. or slightlylower, provided this initial low temperature stage is employed. Theformaldehyde is then added in a suitable form. For reasons pointed outwe prefer to use a solution and whether to use a commercial 37%concentration is simply a matter of choice. 'In large scalemanufacturing there may be some advantage in using a 30% solution offormaldehyde but apparently this is not true on a small laboratory scaleor pilot plant scale. 30% formaldehyde may tend to decrease anyformaldehyde loss or make it easier to control unreacted formaldehydeloss.

On a large scale if there is any diificulty with formaldehyde losscontrol, one can use a more dilute form of formaldehyde, for instance, a30% solution. The reaction can be conducted in an autoclave and noattempt made to remove water until the reaction is over. Generallyspeaking, such a procedure is much less satisfactory for a number ofreasons. For example, the reaction does not seem to go to completion,foaming takes place, and other mechanical or chemical difficulties areinvolved. We have found no advantage in using solid formaldehyde becauseeven here water of reaction is formed.

Returning again to the preferred method of reaction. and particularlyfrom the standpoint of laboratory procedure employing as glass resinpot, when the reaction has proceeded as one can reasonably expect at alow temperature, for instance, after holding the reaction mass with orwithout stirring, depending on whether or not it is homogeneous, at 30or 40 C., for 4 or S'hours, or at the most, up to 10-24 hours, we thencomplete the reaction by raising the temperature up to 150 C., orthereabouts as required. Theinitial low temperature procedure can beeliminated or reduced to merely the shortest period of time which avoidsloss of amine or formaldehyde. At a higher temperature we use aphaseseparating trap and subject the mixture to reflux condensationuntil the water of reaction and the water of solution of theformaldehyde is eliminated. We then permit the temperature to rise tosomewhere about C., and generally slightly above 100 C., and below C.,by eliminating the solvent or part of the solvent so the reaction massstays within this predetermined range. This period of heating andrefluxing, after the water is eliminated, is continued until thereaction mass is homogeneous and then for one to three hours longer. Theremoval of the solvents is conducted in a conventional manner in thesame way as the removal of solvents in resin manufacture as described inaforementioned U. S. Patent No. 2,499,368.

Needless to say, as .far as the ratio of reactants goes we haveinvariably employed approximately one mole of the resin based on themolecular weight of the resin molecule, 2 moles of the secondary amineand 2 moles of formaldehyde. In some instances we have added a trace ofcaustic as an added catalyst but have found no particular advantage inthis. In other cases we have used a slight excess of formaldehyde and,again,.have not found any particular advantage in this. In other cases,we have used a slight excess of amine, and, again, have not found anyparticular advantage in so doing. Whenver feasible we have checked thecompleteness of reaction in the usual ways, including the amount ofwater of reaction, molecular weight, and particularly in some instanceshave checked whether ornot the end-product showed surfaceactivity,particularly in a dilute acetic acid, solution. The

' nitrogen content after removal of unreacted amine, if

any is present, is another index.

15 In*light of what has" been said previously, little more" nee'd'besaid as to theactuafprocedure employed'for'the preparation of the hereindescribed condensation products. The followingexamplewill serve by wayof illustration.

Example 1b The phenol-aldehyde resin i s the' one that has beenidentified previously as: Example 1a. It was obtained fromapara-tertiary bu tylphenol-and formaldehyde. The resin was=preparedusing an acid catalyst which was completely neutralized at the end of"the reaction. The molecular weight of the resin was 882.5. Thiscorresponded to an average of'about-3 /z phenolic nuclei, as the valuefor n which excludes the 2' external nuclei, i. e., the resin waslargely a'mixturehaving 3 nuclei'and 4 nuclei; excluding the-2 externalnuclei, or 5 and 6 overall nuclei. The resin so obtained in aneutralstate had a light amber color.

882 gramsof the-resin identified as lax-preceding were powdered andmixed with 700* grams of xylene. The

mixture was refluxed until solution was complete. It was them adjustedto approximately 30 to'35" C. and 210 grams of diethanolamineaddedlThe-mixture was stirred vigorouslyand formaldehyde" added slowly: Theformaldehyde used was a-'37% solution and 160 grams were employed whichwereaddedin about 3hours; mixture was stirred vigorously and keptwithin" a temperaturerange of 30 to 45 'C., for about'Zl hours. At theend of this period of time it was refluxed, using a phase-separatingtrap and a small'amount of aqueous distillate withdrawn from time totime and the presence ofunreacted formaldehyde notedl Any unreactedformaldehyde seemed to disappear within approximately 3" The hours afterthe refluxing was started. As soon as the odor of formaldehyde was nolonger detectible the phaseseparating trap was set so as to eliminateall water of solution and reaction. After the water was eliminated partof the xylene was rernoveduntil the temperature reached about 150 C. Themass was kept at this higher temperature for about 3% hours and reactionstopped. During this time any additionalwater, which was probably waterof reaction whichhadformed; was eliminated by means of the trap. Theresidual xylene was permitted to stay in the cogeneric mixture. A smallamount of the sample was heated on a water bath to remove the excessxylene'and'the residual material was dark red in color and had theconsistency of a sticky fluid or a tacky resin. The overall reactiontime was a little over hours. In other instances it has varied fromapproximately 24 to 36 hours. The time can be' reduced by cutting thelow temperature period to about 3 to 6 hours.

Note that in Table II following thereare alarge number of added examplesillustrating the same procedure. In eachcase the initial mixturewasstirred'and held at a fairly low temperature (30to40" C.) for aperiod of several hours. Then refluxingwa'semplo'yed until the odor offormaldehyde disappeared. After the odor of formaldehyde'disappeared thephase-separating trap was employed ,to separate out all thewater, boththe solutionand condensation. Afterall the water had been separatedenough xylene wastaken out to have the final product reflux forseveralhours somewhere in the range of 145 to 150 C., or thereabouts.Usually the mixture yielded a clear solution by the time the bulk of thewater, orall of the water, had been removed.

Note'that as pointed out previously, this procedure is illustrated by 24examples in Table H.

Table II Strength of Reac- Reac- Max. Ex. Resin Amt, tormal- Solventused tlou tion dis- No. used grs. Amine used and amount dehyde and amt.temp time, till.

soln. and 0. (hrs) temp.,

amt. 0.

882' Diethanolamlne, 210g 37%, 162 g... Xylene, 700 g..- 22-26 32 137480 Diethanolarnine, g. 37%, 81 g Xylene, 450 g..- 21-23 28 150 633'..do do Xylene, 600 gm. 20-22 36 441 'Dlpropanolamine, 133 g. 30%, 100g... Xylene, 400 g.--. 20-23 34 146 (1 do Xylene, 450 g 21-23 24 141Xylene, 600 g 21-28 24 145 V me, 178 Xylene, 700 g 20-26 24 152 480Ethylethanolamine, 89 g Xylene, 450 g. 24-30 28 151 9b. 8a-.- 633' do; eXylene, 00 g. 22-25 27 147 10b 11m... 473 Cyclohexylethanolamlne, 143 gXylene, 450 g. 21-31 31 140 110.-.- 1212.--. 511 do d0 22-23 30 14812b.. 13m... 665 -do "do Xylene, 550 g..-. 20-24 27 152 CzHrOCzHiOCgHs13b 1a.-- 441 NH, 176 g do Xylene, 400 g 21-25 24 160 'czHsoczHioczHs1415-.-. 3a..- 480 NH, 176 g do Xylene. 450 g.... 20-26 26 146 HOCIH4CgH OC H4OC2H| 15b 7a..-" 595 NH, 176 g do Xylene, 550 g. 21-27 30 147HOCzHs HOCzH OC H OCzH4 160.--. 1a---.- 441 NH, 192 g do Xylene, 400 g20-22 30 148 HOG: 4

HOCzHrOCzHsOCzHt 170.--- 3a.. 480 NH, 192 g do do 20-25 28 HOCzHsHOCzH-rOCzHsOCsHt 181)-. 120.... 511 NH, 102g do Xylene, 500 g. 21-24 3149 Ex. Resin Amt, Amineused and amount i r rfi i i Solventused Elixir?:1 No. used grs. hyde soln. and amt. tem time, temp.,

and amt. hrs. 0.

HOO2H4OC2H4OC2HA 1912.-.- 2011.... 498 NH, 192g 37%,81g. Xy1ene,450g-22-25 -32 1 15B HOCzH;

C a( a 4)a 7 a... 21a. 542 N ofi %,100 g-.. Xylene, aoogm. 21-23 as I 151v OH8(OO2H4)3 541 NH, 205 g do has 2:930 34 14s HOC9H4 CHa(OOrH4)s221).... la. 441 NH,206g do Xylene, 400 g.. 22-23 31 145 Boom. v 33211::$3113: 33? 5335233335553;i8?)E:j:33::11331333331111: 33521255231:i21381111 iii? it ii? PART 5 Cognizance should be taken of oneparticular feature in connection with the reaction involving thepolyepoxide and the amine condensate and that is this; the aminemodifiedphenol-aldehyde resin condensate is invariably basic and thus one neednot add the usual catalysts which are used to promote such reactions.Generally speaking, the reaction will proceed at a satisfactory rateunder suitable conditions without any catalyst at all.

Employing polyepoxides in combination with a nonbasic reactant the usualcatalysts include alkaline materials such as cautic soda, causticpotash, sodium methylate, etc. .Other catalyst may be acidic in natureand are of the kind characterized by iron and tin chloride. Furthermore,insoluble catalysts such as clays or specially prepared mineralcatalysts have been used. If for any reason the reaction did not proceedrapidly enough with the diglycidyl ether or other analogous reaction,then a small amount of finely divided caustic soda or sodium methylatecould be employed as a catalyst. The amount generally employed would bel%-or 2%.

It goes without saying that the reaction can take place in an inertsolvent, i. e., one that is not oxyalkylation-susceptible. Generallyspeaking, this is most conveniently an aromatic solvent such as xyleneor a higher boiling coal tar solvent, or else a similar high boilingaromatic solvent obtained from petroleum. One can employ an oxygenatedsolvent such as the diethylether or ethylene glycol, or the diethyletherof propylene glycol, or similar ethers, either alone or in combinationwith a hydrocarbon solvent. The selection of the solvent depends in parton the subsequent use of the derivatives or reaction products. If thereaction products are to be rendered solventfree and it is necessarythat the solvent be readily removed as, for example, by the use ofvacuum distillation, thus xylene or an aromatic petroleum will serve.

Example 10 The product was obtained by reaction between the diepoxidepreviously designated as diepoxide A, and condensate 2b. Condensate 2bwas derived from resin 3a.

The solution of the condensate in xylene was adjustedto a" 50% solution.In this particular instance, and in practically all the others whichappear in the subsequent tables, the examples are characterized by thefact that i no alkaline catalyst was added. The reason is, of course,If'de that the condensate as such is strongly basic. sired, a smallamount of an alkaline catalyst could be added, such as finely powderedcaustic, soda, sodium methylate, etc. If such alkaline catalyst is addedit may speed up the reaction but it may also cause an undesire ablereaction, such as the polymerization of the diepoxide.

In any event, 119 grams of the condensate dissolved in an equal weightof xylene were stirred and heated to about 105 C. 18.5 grams of thediepoxide previously indentified as diepoxide A, and dissolved in anequal product was allowed to reflux at .a temperature in theneighborhood of 130 C. to 132 C., using "a'phase-sep arating trap. Asmall amount of xylene was removed by means of the phase-separating trapso thatlthe refluxing vtemperature rose gradually to .a maximum of 175.C.

Resin 3a, in turn, was obtained from tertiary amylphenol The mixture wasrefluxed at C. for approximately 3 /2 vhours, with the total reactiontime being 4.5 hours.

the physical properties. The material was a dark red viscous semi-solid.-It was insoluble in water, it wasinsoluble in 5% gluconic acid, auditwas soluble in' xylene,

and particularly in a mixture of 80% xylene and 20% methanol. However,if the material Was-dissolved'in an oxygenated solvent and then shakenwith 5% gluconic acid it showed a definite tendency to disperse,suspend,

"or form a so], and particularly in a xylene-methanol mixed solvent aspreviously described, with or without the further addition of a littleacetone. I

The procedure employed of course is simple in light of what has beensaid previously and in effect is a proce: v dure similar to thatemployed in the use of glycide or methylglycide as oxyalkylating agents.See, for example, Part 1 of U. S. Patent No. 2,602,062 dated July 1, 2,1

to De Groote.

Various examples obtained in substantially the same a manner areenumerated in the following tables:

20 the amount of catalyst used, or reduce the temperature of reaction byadding a small amount of initially lower Table III Diep- Time Max 113x.116;).- Amt., oxide Amt", Xylene, Moiliar oi 1reactemp Color andphysical state 0. ea c grs. g'rs. grs. re on used used hrs. 0

119 A 18.5 137. 2:1 4. 5 175 Darlrdbrown viscous semi- SO 1 125 A 18. 5143. 5 2: 1 5 170 D0. 108 A 18. 5 126. 5 2: 1 4 170 Do. 116 A 18. 5 134.5 2: 1 4 176 Do. 126 A 18. 5 144. 5 2: 1 5 182 D0. 164 A 18. 5 182. 5 2:1 5 172 D0. 126 A 18.5 1441 5 2: 1 5 174 D0. 143 A. 18. 5 161. 5 2: 1 5180 D0. 140 A 18. 5 158. 5 2:1 5 182 D0. 152 A 18. 5 170. 5 2: 1 5 185D0.

Table IV Con- Diep Time Max 1131:. dei- Amt., oxide Amt., Xylene, Molaroiireactemp Color and physical state 0. sa 0 grs. grs. g'rs. ratio onused used hrs; a Q

119 B 11 130 2:1 4 180 Darfidbrown viscous semiso 125 B 11 136 2:1 5 178D0. 108 B 11 119 2:1 4 182 Do. 116 B 11 127 2:1 4. 5 185 D0. 126 B 11137 2:1 4 180 D0. 164 B 11 175 2:1 5 175 D0. 126 B 11 137 2: 1 4. 5 184Do. 143 B 11 154 2:1 5 176 D0. 140 B 11 151 2:1 4 181 Do. 152 B 11 1622: 1 5 185 D0.

Solubility in regard to all these compounds was subboiling solvent suchas benzene, or use benzene entirely.

stantially similar to that which was described in Ex- 35 ample 10.

Table V Probable Resin congfw g Amt. 0t Amt. of number of Ex. No.densgte rectio'n product, solvent, hydroxyls use grs. grs. per moeproduct cule Table VI Probable Resin conggfw g Amt. of Amt. of numberof Ex. No. densgte rea'cfio'n product, solvent, hydroxlyls use grs. grs.per mo eproduct mile At times we have found a tendency for an insolublemass to form or at least to obtain incipient cross-linking or gellingeven when the molal ratio is in the order of 2 moles of resin to one ofdicpoxide. We have found this can be avoided by any one of the followingprocedures or their equivalent. Dilute the resin or the diepoxide, orboth, with an inert solvent, such as xylene or the like. In someinstances an oxygenated solvent such as the diethyl ether ofethyleneglycol may be employed. Another procedure which is helpful is toreduce Also, we have found it desirable at times to use slightly lessthan apparently the theoretical amount of diepoxide, for instance orinstead of The reason for this fact may reside in the possibility thatthe molecular weight dimensions on either the resin molecule or thediepoxide molecule may actually vary from the true molecular weight byseveral percent.

Previously the condensate has been depicted in a simplified form which,for convenience, may be shown thus:

(Amine)CH (Resin) CH (Amine) Following such simplification the reactionproduct with a polyepoxide and particularly a diepoxide, would beindicated thus:

[(Amine) CHz(Resin) 0H1 (Amine)] [D.G.E.]

[(Amine) CHn(Resin) CHz(Amiue)] in which D. G. E. represents adigylcidyl ether as specified. If the amine happened to have more thanone reactive hydrogen, as in the case of a hydroxylated amine [(Resin)]All the above indicates the complexity of the reaction product obtainedafter treating the amine-modified resin condensate with a polycpoxideand particularly diepoxide as herein described.

PART 6 The preparation of the compounds or products described in Part 5,preceding, involves anoxyalkylating agent, to wit, a polyepoxide andusually a diepoxide. The procedure described in the present part is afurther oxyalkylation step but involves the use of a monoepoxide or theequivalent. The principal difierence is only that while polyepoxides areinvariably nonvolatile and can be reacted under a condenser, at leastnumerous monoepoxides and particularly ethylene oxide, propylene oxide,butylene oxide, etc., involve somewhat different operating conditions.Glycide and methylglycide react under practically the same conditions asthe polyepoxides. Actually, for purpose of convenience, it is mostdesirable to conduct the previous reaction, i. e., the one involving thepolyepoxide in equipment such that subsequent reaction with monoepoxidemay follow without interruption. For this reason considerable is said indetail as to oxyethylation, etc.

Although ethylene oxide and propylene oxide may represent less of ahazard than glycide, yet these reactants should be handled with extremecare. One suitable procedure involves the use of propylene oxide orbutylene oxide as a solvent as Well as a reactant in the earlier stagesalong with ethylene oxide, for instance, by dissolving the appropriateresin condensate in propylene oxide even though oxyalkylation is takingplace to a greater or lesser degree. After a solution has been obtainedwhich represents the selected resin condensate dissolved in propyleneoxide or butylene oxide, or a mixture which includes the oxyalkylatedproduct, ethylene oxide is added to react with the liquid mass untilhydrophile properties are obtained, if not previously present to thedesired degree. Indeed, hydrophile character can be reduced or balancedby use of some other oxide, such as propylene oxide or butylene oxide.Since ethylene oxide is more reactive than propylene oxide or butyleneoxide, the final product may contain some unreacted propylene oxide orbutylene oxide which can be eliminated by volatilization or distillationin any suitable manner. See article entitled Ethylene Oxide Hazards andMethods of Handling, Industrial and Engineering Chemistry, volume 42,No. 6, June 1950, pp. 125l1258. Other procedures can be employed as, forexample, that described in U. S. Patent No. 2,586,767, dated February19, 1952, to Wilson.

The amount of monoepoxides employed may be as high as 50 parts ofmonoepoxide for one part of polyepoxide treated amine-modifiedphenol-aldehyde condensation product.

Example 1D The polyepoxide-derived oxyalkylation-susceptible compound isthe one previously designated as 10. Polyepoxide-derived condensate 10was obtained, in turn, from condensate 2b and diepoxide A. Reference toTable II shows the composition of condensate 2b. Table II shows it wasobtained from resin 5a, diethanolarnine and formaldehyde. Table I showsthat resin 5a was obtained from tertiary amylphenol and formaldehyde.

For the purpose of convenience, reference herein and in the tables tothe oxyalkylation-susceptible compound will be abbreviated in the tableheading as OSC; reference is to the solvent-free material since, forconvenience, the amount of solvent is noted in a second column.Actually, part of the solvent may have been present and in practicallyevery case was present in either the resinification process or thecondensation process, or in treatment with a polyepoxide. In any event,the amount of solvent present at the time of treatment with amonoepoxide is indicated, as stated, on a solvent-free basis.

13.75 pounds of the polyepoxide-derived condensate were mixed with 13.75pounds of solvent (xylene in this series), along with one pound offinely powdered caustic soda as a catalyst. The reaction mixture wastreated with 13.75 pounds of ethylene oxide. At the end of the reactionperiod the molal ratio of oxide to initial compound was approximately62.5 to one, and the theoretical molecular weight was approximately5500.

130 C., and the pressure 10 to 15 pounds.

..Adjustrnent was made in the autoclave to operate *at' a temperature ofabout C. to C., and at a pressure of 10 to 15 pounds per square inch.

The time regulator was set so as to inject the oxide in approximatelyone hour and then continue stirring for a half hour longer, simply as aprecaution to insure complete reaction. The reaction went readily and,as a matter of fact, the ethylene oxide probably could have beeninjected in 30 minutes instead of an hour and the subsequent timeallowed to insure completion of reaction may have been entirelyunnecessary. The speed of reaction, particularly at low pressure,undoubtedly was due in a-large measure to the excellent agitation andalso to the comparatively high concentration of catalyst.

A comparatively small sample, less than 50 grams, was withdrawn merelyfor examination as far as solubility or emulsifying power was concerned,and also for the purpose of making some tests on various oil fieldemulsions. The amount withdrawn was so small that no cognizance of thisfact is included in the data or subsequent data, or in data reported intabular form in subsequent Tables VII, VIII and IX.

The size of the autoclave employed was 35 gallons. In innumerableoxyalkylations we have withdrawn a substantial portion at the end ofeach step and continued oxyalkylation on a partial residual sample. Thiswas not the case in this particular series. Certain examples wereduplicated as hereinafter noted and subjected to oxyalkylation with adifferent oxide.

Example 2D This simply illustrates further oxyalkylation of .Example 1D,preceding. The oxyalkylation-susceptible compound 10 is the same as theone used in Example 1D, preceding, because it is merely a continuation.In subsequent tables, such as Table VII, the oxyalkylationsusceptiblecompound in the horizontal line concerned with Example 2D refers tooxyalkylation-susceptible compound lC. Actually, one could refer just asproperly to Example ID at this stage. It is immaterial which designationis used so long as it is understood such practice is used consistentlythroughout the tables. In any event, the amount of ethylene oxideintroduced was less than previously, to wit, only 5.5 pounds. This meantthe amount of oxide, at the end of the stage was 19.25 pounds, and theratio of oxide to oxyalkylation-susceptible compound (molar basis) atthe end was 87.5 to 1. The theoretical molecular weight was 6600. Therewas no added solvent. In other words, it remained the same, that is,13.75 pounds and there was no added catalyst. The entire procedure wassubstantially the same as in Example 1D, preceding.

In this, and in all succeeding examples, the time and pressure were thesame as previously, to wit, 125 to The time element was only one-halfhour because considerable less oxide was added.

Example 3D The oxyalkylation proceeded in the same manner as in Examples1D and 2D. There was no added solvent and no added catalyst. The amountof oxide added was 5.5 pounds. Thetotal amount of oxide at the end ofthe stage was 24.75 pounds. The molal ratio of oxide to condensate was112.5 to l. The theoretical molecular weight was approximately 7700, andas previously noted the time period, temperature and pressure were thesame as in preceding Example 2D.

Example 4D The oxyalkylation was continued and the amount of oxide addedwas the same as before,'to wit, 5.5 pounds, The amount of oxide added atthe end of the reaction was 30.25 pounds. There was no added solvent andno added catalyst. Conditions as far as temperature and pressureareuconcerned were the same asjn previous. examples 7 previously, towit, one hour.

23 The time period was slightly longer, to wit, 45 minutes. The reactionat this point showed modest, if any, tendency to slow up. The molalratio of oxide to oxyalkylation-susceptible compound was 137.5 to 1. Thetheoretical molecular weight was 8800.

Example D The oxyalkylation was continued with the introduction ofanother 5.5 pounds of oxide. No added solvent was introduced andlikewise no added catalyst was introduced. The theoretical molecularweight at the end of the re action was approximately 9900. The molalratio of oxide to oxyalkylation-susceptible compound was 162.5 to 1. Thetime period was the same as before.

Example 6D .The same procedure was followed as in the previous exampleswithout the addition of either more catalyst or more solvent. The amountof oxide added was the same as before, to wit, 5.5 pounds. The amount ofoxide at the end of the reaction was 41.25 pounds. The time required tocomplete the reaction was slightly more than At the end of the reactionperiod the ratio of oxide to oxyalkylation-Snsceptible compound was187.5 to 1, and the theoretical molecular weight was 11,000.

The same procedure as described in the previous examples was employed inconnection with a number of the other condensations describedpreviously. All these data have been presented in tabular form in TablesVII through XII.

In substantially every case a 35-gallon autoclave, was employed,although in some instances the initial oxyethylation was started in a15-gallon autoclave and then transferred to a 25-gallon autoclave, or attimes to the 35-ga1lon autoclave. This is immaterial but happened to bea matter of convenience only. The solvent used in all cases was xylene.The catalyst used was finely powdered caustic soda.

Referring to Tables VII, VIII and IX, it will be noted that compounds 1Dthrough 18D were obtained by the use of ethylene oxide, whereas Examples19D through 36D were obtained by the use of propylene oxide; andExamples 37D through 54D were obtained by the use of butylene oxide.

Referring now to Table VIII specifically, it will be noted that theseries of examples beginning with IE were obtained, in turn, by use ofboth ethylene and propylene oxides, using ethylene first; in fact, usingExample 2D as the oxyalkylation-susceptible compound. This applies toseries 1E through 18E.

Similarly, series 19E through 36E involve the use of both propyleneoxide and ethylene oxide in which the propylene oxide was used first, towit, 19E was prepared from 24D, a compound which was initially derivedby use of propylene oxide.

Similarly, Examples 37E through 54E involve the use of ethylene oxideand butylene oxide, the ethylene oxide being used first. Also, these twooxides were used in the series 55E through 72E, but in this latterinstance the butylene oxide was used first and then the ethylene oxide.

Series 73E through 90E involve the use of propylene oxide and butyleneoxide, butylene oxide being used first and propylene oxide being usednext.

In series 1F through 18F the three oxides were used. It will be noted inExample IF the initial compound was 77E; Example 77E, in turn, wasobtained from a compound in which butylene oxide was used initially andthen propylene oxide. Thus, the oxide added in the series 1F through 6Fwas by use of ethylene oxide as indicated in Table IX.

Referring to Table IX, in regard to Example 19F it will .be noted againthat the three oxides were used and 1917 was obtained from 5713. Example57E, in turn, was obtained by using butylene oxide first and thenethylene oxide. In Example 19F and subsequent examples, such as 20F,21F, etc., propylene oxide was added.

Tables X, )G and XII give the data in regard to the oxyalkylationprocedure as far as temperature and pressure are concerned and also givesome data as to solubility of the oxyalkylated derivative in water,xylene and kerosene.

Referring to Table VII in greater detail, the data are as follows: Thefirst column gives the example numbers, such as 1D, 2D, 3D, etc. etc.,the second column gives the oxyalkylation-susceptible compound employedwhich, as previously noted in the series 1D through 6D, is Example is,although it would be just as proper to say that in the case of 2D theoxyalkylation-susceptiblc compound was 1D, and in the case of 3D theoxyalkylationsusceptible compound was 2D. Actually, reference is to theparent derivative for the reason that the figure stands constant andprobably leads to a more convenient presentation. Thus, the third columnindicates the epoxidederived condensate previously referred to.

The fourth column shows the amount of ethylene oxide in the mixtureprior to the particular oxycthylation step. In the case of Example 1Dthere is no oxide used but it appears, of course, in 2D, 3D, and 4D,etc.

The fifth column can be ignored for the reason that it is concerned withpropylene oxide only, and the sixth column can be ignored for the reasonthat it is concerned with butylene oxide only.

The seventh column shows the catalyst which is invariably powderedcaustic soda.

The eighth column shows the amount of solvent which is xylene unlessotherwise stated.

The ninth column shows the oxyalkylation-Snsceptible compound which inthis series is the polyepoxide-derived condensate.

The tenth column shows the amount of ethylene oxide in at the end of theparticular step.

Column eleven shows the same data for propylene oxide and column twelveshows data for butylene oxide. For obvious reasons these can be ignoredin the series 1D through 18D.

Column thirteen shows the amount of the catalyst at the end of theoxyalkylation step, and column fourteen shows the solvent at the end ofthe oxyalkylation step.

The fifteenth, sixteenth and seventeenth columns are concerned withmolal ratio of the individual oxides to the oxyalkylation-susceptiblecompound. Data appears only in column fifteen for the reason, previouslynoted, that no butylene or propylene oxide were used in the presentinstance.

The theoretical molecular weight appears at the end of the table whichis on the assumption, as previously noted, as to the probable molecularweight of the initial compound, and on the assumption that all oxideadded during the period combined. This is susceptible to limitationsthat have been pointed out elsewhere, particularly in the patentliterature.

Referring now to the second series of compounds in Table VII, to wit,Examples 19D through 36D, the situation is the same except that it isobvious that the oxyalkylating agent used was propylene oxide and notethylene oxide. Thus, the fourth column becomes a blank and the tenthcolumn becomes a blank and the fifteenth column becomes a blank, butcolumn five, which previously was a blank in Table VII, Examples 1Dthrough 18D, now carries data as to the amount of propylene oxidepresent at the beginning of the reaction. Column eleven carries data asto the amount of propylene oxide present at the end of the reaction, andcolumn sixteen carries data as to the ratio of propylene oxide to theoxyalkylation-susceptible compound. In all other instances the variousheadings have the same significance as previously.

Similarly, referring to Examples 37D through 54D in Table VII, columnsfour and five are blanks, columns ten and eleven are blanks, and columnsfifteen and six-t3 teen are blanks, but data appears in column six as tobutylene oxide present before the particular oxyalkylation step. Columntwelve gives the amount of butylene oxide present at the end of thestep, and column seventeen gives the ratio of butylene oxide tooxyalkylationsusceptible compound. 1

Table VIII is in essence the data presented in exactly the same wayexcept the two oxides appear, to wit, ethylene oxide and proylene oxide.This means that there are only three columns in which data does notappear, all three being concerned with the use of butylene oxide. firstby the very fact that reference to ExamplelE, in turn, refers to 2D, andalso shows that ethylene oxide was ,present at the very first stage.Furthermore, for ease of comparison and also to be consistent, the dataunder Molal Ratio in Regard to ethylene oxide and propylene oxide goesback to the original diepoxide derived condensate 10. cause the figures87.5 and 47.4 coincide with the figures for 2D derived from 10 as shownin Table VII.

.In Table VHI (Examples 19E through 36E) the same Furthermore, it showswhich oxide was used Thisis obvious, of course, be-

5 such as 37B and subsequent examples where the two oxides used areethylene oxide and butylene oxide, and the table makes it plain thatethylene oxide was used first. Inversely, Example 55B and subsequentexamples show the use of the same two oxides but with butylene oxidebeing used first as shown on the table.

Example 73E and subsequent examples relate to the use of propylene oxideand butylene oxide. Examples beginning with 1F, Table IX, particularly2F, 3F, etc, show the use of all three oxides so there are no blanks asin the first step of each stage where one oxide is missing. It is notbelieved any further explanation need be offered in regard to Table IX.a

As previously pointed out certain initial runsusing one oxide only, orin some instances two oxides, had to be duplicated when usedsubsequently for. further reaction.

It would be confusing to refer; to too much detail in these varioustables for the reason that all the data appear in considerable detailand is such that all results can be readily shown.

Table VII Composition before Composition at end Oxides Oxides Molalratio Ex. No. 080, Cata- Sol- Cata- Sol- Theo ex. 080, lyst, vent, 0S0,lyst, vent, EtO PrO BuO mol. No. lbs. EtO, PrO, BuO, lbs. lbs. lbs, EtO,PrO, BuO, lbs. lbs. to oxyto oxyto oxywt.

lbs. lbs. lbs. lbs. lbs. lbs. alkyl alkyl. alkyl.

suscept. suscept. suscept. compd. compd.

- 14. 14. 14. 14. 12. 12. 12. 12. 12. 1 l2. 12. 13. 13. 13. 75 13. 7513. 27. 50 13. 75 13. 33. 0 13. 75 13. 38. 5 13. 75 13. 44. 0 13. 75 14..4.. 14.35 14. 14. 14. 35 14. 28. 70 14. 35 14. 34. 14. 35 14. 40. 2 I14. 35 14. H 45. 95 14. 35 12. l2. l5

qooowoeemo owwqwqwq cnwwqr tncnv qwwmmtnmm llllllllllllllll cnen TableIX Composition before Composition at and E Oxides Oxides Molal ratio x.No. 080, Oata- Sol- Cata- Sol- Theo.

ex. 080, lyst, vent, S0, lyst, vent, EtO PrO BuO mol. No. lbs. EtO, PrO,B110, lbs. lbs. lbs. EtO, PrO, BuO, lbs. lbs. to oxyto oxyto oxywt.

lbs. lbs. lbs. lbs. lbs. lbs. alkyl. alkyl. alkyl.

. Suscept. suscept. suscept. compd. compd. compd.

Reference to solvent and amount of alkali at any point takes intoconsideration the solvent from the previous step and the alkali leftfrom this step. As previously pointed out, Tables X, XI and X11 giveoperating data in connection with the entire series, comparable to whathas been said in regard to Examples 1D through 45 The colors of theproducts usually vary from a reddish amber tint to a definitely red, andamber, or a straw color or even a palezstraw color. The reason isprimarily. that no efiort ismade to obtain colorless resins initiallyand the resins themselves may be yellow, amber,

50 or even dark amber. Condensation of a nitrogenous The productsresulting from these procedures may c611 tain modest amounts, or havesmall amounts, of the solvents as indicated by the figures'in the tables If desired, the solvent may be removed by distillation,-andparticularly vacuum distillation. Such distillation .also may removetraces or small amounts of uncombined oxide, if present and volatileunder the conditions .employed.

Obviously, in the use of ethylene oxide and propylene oxide incombination one need not first use one oxide and then the other, but onecan mix the two oxides and thus obtain what may be termed anindifieli'ent oxyalkylation, i. e., not attempt to selectively add oneand then the other, or any other variant.

product invariably yields' a darkerproduct than the original resin andusually has a reddish color. The solventemployed, if xylene, addsnothing to the color --but one may use a darker colored aromaticpetroleum solvent. Oxyalkylation generally tends to yield lightercolored products and the more oxide'employed the lighter theloolor ofthe product. Products can be prepared in jjwhich'the final color is alighter amber with a reddish tint. Such products can be decolorized bythe use of clays, bleaching chars, etc. As far as use in demulsificationis concerned, or'some other industrial uses, there is no justificationfor the cost of bleaching the product. Generally speaking, the amount ofalkaline catalyst present is comparatively small and it need not be re-Needless to say, one could start with ethylene oxide and then usepropylene oxide, and then go back to ethylene oxide; or, inversely,start with propylene oxide,

then use ethylene oxide, and then go back to propylene drochloric acid,for example, to neutralize the alkalinity ethylene oxide and butyleneoxide, or butylene-oxideand propylene oxide.

moved. Since the products per se are alkaline due to the presence; of abasic nitrogen, the removal of the alkaline catalyst-is somewhat moredifiicult than or-' jfdinarily is the case for the reason that if oneadds byone may partially neutralize the basic nitrogen radical also.Thepreferred procedureis to ignore the presence Table X Max. Max.Solubility Ex. temp., pres., Time, No. 0. p. s. i. hrso Water XyleneKerosene 10-15 1 Emulslfiable Insoluble. 10-15 Do. 10-15 Do. 10-15 D0.10-15 Do. lO-15 Do. 10-15 Do. 10-15 D0. 10-15 D0. 10-15 Do. 10-15 D0.10-15 Do. 10-15 Do. 10-15 Do. 10-15 Do. 10-15 D0. 10-15 D0. 10-15 Do.10-15 Du. 10-15 Do. 10-15 Do. 10-15 Do. 10-15 Soluble. 10-15 D0. 10-15Insoluble. 10-15 Do. 10-15 Do. 10-15 D0. 10-15 Soluble. 10-15 o Do 10-15do Insoluble. 10-15 D 10-15 10-15 10-15 10-15 10-15 10-15 10-15 10-1510-15 10-15 10-15 10-15 10-15 10-15 10-15 10-15 10-15 10-15 10-15 10-1510-15 10-15 Table XI Max Solubility pres Time, p. s. 1 hrs.

Water Xylene Kerosene 10-15 Emulslfiable. Insoluble. 10-15 do Do. 10-15D0. 10-15 D0. 10-15 Do. 10-15 Do. 10-15 D0. 10-15 D0. 10-15 D0. 10-15D0. 10-15 Do. 10-15 D0. 10-15 D0. 10-15 D0. 10-15 D0. 10-15 D0. 10-15D0. 10-15 D0. 10-15 Soluble 10-15 D 10-15 Insoluble. 10-15 D0. 10-15 DO.10-15 D0. 10-15 Soluble 10-15 Insoluble. 10-15 DO. 10-15 Do. 10-15 Do.10-15 D0. IO-la Soluble. 10-15 Insoluble. 10-15 D0. 10-15 Do. 10-15 Do.10-15 D0. 10-15 D0,.

Table X1 Coutinued Max. Max. Solubility Ex. temp, pres., Time, No. O. p.s. i. hrs.

Water Xylene Kerosene Emulsifiab1e So1uble Insoluble.

d (1 Do.

&

Table XII Time, hrs.

Solubillty Water Kerosene Soluble. Do.

Do. Insoluble.

Do. Do. Soluble. D0. Insoluble,

35 PART 7 As to the use of conventional demulsifying agents reference ismade to U. S. Patent No. 2,626,929, dated January 7, 1953, to De Groote,and particularly to Part- Three. Everything that appears therein applieswith equal force and effect to the instant process, noting only 7 thatwhere reference is made to Example 13b in said text beginning in column15 and ending in column 18, reference should be to Example 36E, hereindescribed;

PART 8 The products, compounds or the like, herein described can beemployed for various purposes and particularly for the resolution ofpetroleum emulsions of the waterin-oil type as described in detail inPart 7, preceding.

Such products can be reacted with alkylene imine-s, such as ethyleneimine or propylene imine, to produce cation-active materials. Instead ofan imine one may employ what is a somewhat equivalent material, to wit,a dialkylamino-epoxypropane of the structure wherein R and R" are alkylgroups.

It is not necessary to point out that after reaction with a reactant ofthe kind described which introduces a basic nitrogen atom, the resultantproduct can be employed for the resolution of emulsions of thewater-in-oil type as described in Part Seven, preceding, and also forother purposes described hereinafter.

Referring now to the use of the products obtained by reaction with apolyepoxide and certain specified oxyalkylated products obtained in themanner described in Part Six, preceding, it is to be noted that inaddition to their use in the resolution of petroleum emulsions they maybe used as emulsifying agents for oils, fats, and waxes, as ingredientsin the laundering, scouring, drying, tanning and mordanting industries.They may also be used for preparing boring or metal-cutting oils andcattle dips, as metal pickling inhibitors, and for pharmaceuticalpurposes.

Not only do these oxyalkylated derivatives have utility as such but theycan serve as initial materials for more complicated reactions of thekind ordinarily requiring a hydroxyl radical. This includesesterificaction, etherization, etc. i

The oxyalkylated derivatives may be used as valuable additives tolubricating oils, both those derived from petroleum and syntheticlubricating oils. Also, they can be used as additives to hydraulic brakefluids of the aqueous and non-aqueous types. They may be used inconnection with other processes where they are injected into an oil orgas -well for purpose of removing a mud sheath, increasing the ultimateflow of fluid from the surrounding strata and particularly in secondaryrecovery operations using aqueous flood waters. These derivatives alsoare suitable for use in dry cleaners soaps.

More specifically, such products, depending on the nature of the initialresin, the particular monoepoxide selected, and the ratio of monoepoxideto resin, together with the particular polyepoxide employed, result. ina variety of materials which are useful as wetting agents or surfacetension reducing agents; as detergents, emulsifiers or dispersingagents; as additives for lubricants, both of the natural petroleum typeand the synthetic type, as additives in the flotation of ores, and attimes as aids in chemical reactions insofar that demulsifi cation isproduced between the insoluble reactants. Furthermore, such products canbe used for a variety oflother purposes, including use as corrosioninhibitors, defoarners, asphalt additives, and at times even in theresolution of oil-in-water emulsions. They serve at times as mutualsolvents promoting a homogeneous system from two otherwise insolublephases.

The products herein described can be reacted with polycarboxy acids suchas phthalic acid, or anhydride, maleic acid or anhydride, diglycolicacid, and various j tricarboxy and tetracarboxy acids so as to yieldacyiated derivatives particularly if one employs one mole of thepolycarboxy acid for each reactive hydroxyl radical present in the finalpolyepoxide treated product. Thus, one obtains a comparatively largemolecule in which there is a plurality of carboxyl radicals. Such acidicfractional esters are suitable for the resolution of petroleum emulsionsof the water-in-oil type as herein described.

Having thus described our invention, what we claim as new and desire tosecure by Letters Patent is:

1. A 3-step manufacturing method involving (1) condensation; (2)oxyalkylation with a polyepoxide; and (3) oxyalkylation with amonoepoxide; said first step being that of (A) condensing (a) a fusible,non-oxygenated organic solvent-soluble, water-insoluble, phenolaldehyderesin having an average molecular weight corresponding to at least 3 andnot over 6 phenolic nuclei per resin molecule; said resin beingdifunctional only in regard to methylol-forming reactivity; said resinbeing derived by reaction between a difunctional monohydric phenol andan aldehyde having not over 8 carbon atoms and reactive toward saidphenol; said resin being V; in which R is a saturated aliphatichydrocarbon radical having at least 4 and not more than 24 carbon atomsand substituted in the 2,4,6 position; (b) a basic hydroxylatedsecondary monoamine having up to 32 carbon atoms in 7 any group attachedto the amino nitrogen atom, and

(c) formaldehyde; said condensation reaction being conducted at atemperature sufliciently high to eliminate Water and below the pyrolyticpoint of the reactants and resultants of reaction; and with the provisothat the resinous condensation product resulting from the process beheat stable; followed as a second step by (B) reacting said resincondensate with nonaryl hydrophile polyepoxides containing two terminal1,2-epoxy rings obtained by replacement of an oxygen-linked hydrogenatom in a water-soluble polyhydric alcohol by the radical saidpolyepoxides being free from reactive functional groups other than1,2-epoxy and hydroxyl groups and characterized by the fact that thedivalent linkage uniting the terminal oxirane rings is free from anyradical having more than 4 uninterrupted carbon atoms in a single chain;with the further proviso that said reactive compounds (A) and (B) bemembers of the class consisting of non-thermosetting solvent-solubleliquids and solids melting below the point of pyrolysis; with the addedproviso that the reaction product be a member of the class ofsolvent-soluble liquids and solids melting below the point of pyrolysis;and said reaction between (A) and (B) being conducted below thepyrolytic point of the reactants and the resultants of reaction; andwith the final proviso that the ratio of reactants be 2 moles of thesaid polyepoxide-derived product with a monoepoxide;

said monoepoxide being an alpha-beta alkylene oxide havlng not more than4 carbon atoms and selected from the class "consisting of ethylene"oxide, propylene oxide, butylene 6xide,glyci'd' and methylglycide. I

2. The product obtained'by'flie method described in claim 1.

3. A 3-ste'pmanufacturing method'involving (1) condensation; (2)oxyalkylation with a polyepfoxide; and (3) oxyalkylation with" amaneonds; said first step being that of (A)- condensing (a)" a fusible,non-oxygenated organic solvent-soluble, water-insoluble, plieritilaldeliyde resin having an average molecular Weight corresponding to atleast 3 and not over'6 phenolic nuclei per resin molecule; said resinbeing" difiiiictional only in regard to methylol-forrning reactivity;said resinbe'irigdeiived 'by reaction between a difunc'tional monohy iicphenol and an aldehyde having not over 8 carbon atoms and reactivetoward said phenol; said resin being formed in the substantial absenceof trifunctional phenols; said phenol being of the formula in which R isa saturated aliphatic hydrocarbon radical having at least 4 and not morethan 24 carbon atoms and substituted in the 2,4,6 position; (b) a basichydroxylated secondary monoamine having up to 32 carbon atoms in anygroup attached to the amino nitrogen atom, and formaldehyde; saidcondensation reaction being conducted at a temperature sufiiciently highto eliminate water and below the pyrolytic point of the reactants andresultants of reaction; and with the proviso that the resinouscondensation product resulting from the process be heat stable followedas a second step by (B) reacting said resin condensate with nonarylhydrophile polyepoxides containing at least two 1,2-epoxy rings andhaving two terminal 1,2-epoxy rings obtained by replacement of anoxygen-linked hydrogen atom in a water-soluble polyhydric alcohol by theradical said polyepoxides being free from reactive functional groupsother than 1,2-epoxy and hydroxyl groups and characterized by the factthat the divalent linkage uniting the terminal oxirane rings is freefrom any radical having more than 4 uninterrupted carbon atoms in asingle chain; said polyepoxides being characterized by having presentnot more than 20 carbon atoms: with the further proviso that saidreactive compounds (A) and (B) be members of the class consisting ofnon-thermosetting solvent-soluble liquids and solids melting below thepoint of pyrolysis; with the added proviso that the reaction product bea member of the class of solvent-soluble liquids and solids meltingbelow the point of pyrolysis; and said reaction between (A) and (B)being conducted below the pyrolytic point of the reactants and theresultants of reaction; and with the final proviso that the ratio ofreactants be 2 mols of the resin condensate to 1 mole of thepolyepoxide, and then completing the reaction by a third step of (C)reacting said polyepoxide-derived product with a monoepoxide; saidmonoepoxide being an alpha-beta alkylene oxide having not more than 4carbon atoms and selected from the class: consisting of ethylene oxide,propylene oxide, butylene oxide, glycide and methylglycide.

4. A 3-step manufacturing method involving (1) condensation; (2)oxyalkylation with a diepoxide; and (3) oxyalkylation with amonoepoxide; said first step being; that of (A) condensing.(a) afusible, non-oxygenated organic solvent-soluble, water-insoluble,phenol-aldehyde resin having an average molecular weight correspondingto at least 3 and not over 6 phenolic nuclei per resin vmolecule; saidresin being difunctional only in regard in which R is a saturatedaliphatic hydrocarbon radical having at least 4 and notmor'e than 24carbon atoms and substituted in the2,-4',6 position; (b) a basichydroxylated secondary monoainin'e having up to 32 carbon atoms in anygroup atta'ched'to the amino nitrogen atom, and ('c) formaldehydegsaidcondensation reaction being conducted -at'a temperature sutficie'ntlyhigh to eliminate water and below the pyrolytic point of the reactantsand resul'tant's of reaction; and with the proviso that theresinous'condensation product resulting from the process be heat-stable;followed as a second step by (B) reacting said resin condensate withnonaryl hydrophile diepoxides containing two terminal 1,2-epoxy ringsobtained by replacement of an oxygen-linked hydrogen atom in awatersoluble polyhydric alcohol by the radical said diepoxides beingfree from reactive functional groups other than 1,2-epoxy and hydroxylgroups and characterized by the fact that the divalent linkage unitingthe terminal oxirane rings is free from any radical having more than 4uninterrupted carbon atoms in a single chain; said diepoxides beingcharacterized by having present not more than 20 carbon atoms; with thefurther proviso that said reactive compounds (A) and (B) be members ofthe class consisting of non-thermosetting solvent-soluble liquids andsolids melting below the point of pyrolysis; with.the added proviso thatthe reaction product be a member of the class of liquids and solidsmelting below the point of pyrolysis; and said reaction between (A) and(B) being conducted below the pyrolytic point of the reactants and theresultants of reaction; and with the final proviso that the ratio ofreactants be 2 moles of the resin condensate to 1 mole of the diepoxideand then completing the reaction by a third step of (C) reacting saiddiepoxide-- derived product with a monoepoxide; said monoepoxide beingan alpha-beta alkylene oxide having not more than 4 carbon atoms andselected from the class consisting of ethylene oxide, propylene oxide,butylene oxide, glycide and methylglycide.

5. The method of claim 4 wherein the diepoxide contains at least onereactive hydroxyl radical.

6. A 3-step manufacturing method involving (1) condensation; (2)oxyalkylation with a diepoxide, and (3) oxyalkylation with amonoepoxide; said first step being that of (A) condensing (a) a fusible,non-oxygenated organic solvent-soluble, water-insoluble, phenol-aldehydeI resin having an average molecular weight corresponding to at least 3and not over 6 phenolic nuclei per resin molecule; said resin beingdifunctional only in regard to methylol-forming reactivity; said resinbeing derived by reaction between a difunctional monohydric phenol andan aldehyde having not over 8 carbon atoms and reactive toward saidphenol; said resin being formed in the substantial absence oftrifunctional phenols; said phenol being of the formula in which R is asaturated aliphatic hydrocarbon radical having at least 4 and not morethan 24 carbon atoms and substituted in the 2,4,6 position; (b) abasic'hydroxylated secondary monoamine having up to 32 carbon atoms inany group attached to the amino nitrogen atom, and (0) formaldehyde;said condensation reaction being conducted at a temperature sufiicientlyhigh to eliminate water and below the pyrolytic point of the reactantsand resultants of reaction; and with the proviso that the resinouscondensation product resulting from the process be heat-stable; followedas a second step by (B) reacting said resin condensate with ahydroxylated diepoxy- ,polyglycerol containing two terminal 1,2-epoxyrings and having not more than 20 carbon atoms; with the further provisothat said reactive compounds (A) and (B) be members of the classconsisting of non-thermosetting solvent-soluble liquids and solidsmelting below the point of pyrolysis; with the added proviso that thereaction product be a member of the class of solvent-soluble liquids andsolids melting below the point of pyrolysis; and said reaction between(A) and (B) being conducted below the pyrolytic point of the reactantsand the resultants of reaction;- and with the final proviso that theratio of reactants be 2 moles of the resin condensate to 1- mole of thediepoxide; and then completing the reaction by a third step of (C)reacting said diepoxidederived product with a monoepoxide; saidmonoepoxide being an alpha-beta alkylene oxide having not more than 4carbon atoms and selected from the class consisting of ethylene oxide,propylene oxide, butylene oxide, glycide and methylglycide.

7. The method ofclaim 6 whereinthe polyglycerol derivative has not over5 glycerol nuclei, and the precursory phenol is para-substituted andcontains at least 4 and not over 14 carbon atoms in the substituentgroup, and the precursory aldehyde is formaldehyde, and the total numberof phenolic nuclei in the initial resin are not over 5.

References Cited in the file of this patent UNITED STATES PATENTS

1. A 3-STEP MANUFACTURING METHOD INVOLVING (1) CONDENSATION; (2)OXYALKYLATION WITH A POLYEPOXIDE; AND (3) OXYALKYLATION WITH AMONOEPOXIDE; SAID FIRST STEP BEING THAT OF (A) CONDENSING (A) A FUSIBLE,NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, PHENOLALDEHYDERESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 ANDNOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEINGDIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESINBEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL ANDAN ALDEHYDE HAVING NOT OVER 7 CARBON ATOMS AND REACTIVE TOWARD SAIDPHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OFTRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA